Production of cellulose derivatives



Premium 15, 1941 2,423,883 v UNI E STATES PATENT 7 mm:

James Wotherspoon Fisher, Spondon, near Derby, England, assignor to British Oelanese Limited, London, liingland, a company of Great Britain No Drawing. Application October 11, 1944, Serial No. 558,289. In Great This invention is concemed'with improvements in or relating to the production of cellulose derivatives, and particularly to the production of etheresters of cellulose.

in which both the ether-ester produced, as well Britain November 5, 1943 ether, are soluble. Halogenated hydrocarbons, particularly ethylene dichloride, have been found very suitable as inert solvents when the cellulose ether to be esterified as the original cellulose According tothe present invention ether-esters 6 is a hydrophobe ethyl cellulose, containing, for of cellulose containing the radicles of organic carexample, 2.4 to 2.6 ethyl radicles for CsHroOs unit, boxylic acids comprising at leastsix carbon atoms or other cellulose ether which is soluble in the are producedby esterifying cellulose ethers, parhalogenated hydrocarbon. Pyridine is another ticularly alkyl ethers containing at least two alkyl solvent which may be employed in the esteriilcaradicles per CsHmOs unit of cellulose, with an- '10 tion of such hydrophobe ethers. hydrides of the appropriate acids in the presence An important advantage of the. present invenof metal halides as catalysts. Examples of suittion is that the reaction with the anhydride is able metal halides are ferric and stannic chlorides almost quantitative, the excess of anhydride reand particularly zinc chloride. Preferably they quired over the amount theoretically necessary are used in small proportions based on the weight being usually only about 23-10%. of the cellulose ether and in conjunction with The. cellulose ether-esters with which the insmall proportions of a hydro-halide acid, particuvention is particularly concerned are those oblarly hydrochloric acid. Proportions of metal tained by the esteriflcation of ethyl celluloses and halide and of acid of from ;25 to 1% of the weight other alkyl celluloses which are soluble in hydroof the ether are preferred. phobe organic solvents, for example mixtures of The invention is particularly concerned with toluene and butyl. alcohol, particularly ethyl celthe production of cellulose ether-esters which luloses containing 2.3-2.8 ethoxy radicles per have a low moisture regain 'and'the use of metal CcHroOs unit. Examples f other yl (39111110888 halides as catalysts isof particular value in this which may be ifled are propy butyl and connection. In order to obtain a low moisture hexyl celluloses. As has already been stated the regain it is desirable that cellulose ether-esters anhydrides employed are anhydrides of organic should be substantially free from hydroxy groups, carboxylic acids containing at least six carbon the average value of the sum of the ether and atoms. Preferably they are anhydrides of fatty ester radicles in each Cal-11005 unit of cellulose mono-carboxylic acids containing .12 or more carbeing at least 2.5 and preferably 2.7 or 2.8 or bon atoms in the molecule, for example lauric, more. In order to obtain such a degree of subpalmltic and stearic anhydrides, though anhystitution the choice of esteriiication conditions drides of other carboxylic acids may be employed, is important, since if it is necessary to use vigorfor example the anhydrides of caproic, heptylic 1 cos conditions in order to obtain the required and other aliphatic acids and of benzoic and other degree of esterification there is a risk that degaromatic acids. Y radation may itself make it substantially im- The following example is given to illustrate the possible to obtain the desired properties. Sulinvention: I phuric acid, which is the normal esteriflcation 200 parts by weight of an ethyl cellulose having catalyst, and derivatives thereof, for example 5111- an ethoxy content of about 48%. and soluble in phuryl chloride and sulphonic acids, are undesir- 40 a mixture of toluene and butyl alcohol is disable for use as catalysts since they are liable to solved in 1250 parts of ethylene dichloride. When introduce into the cellulose derivative sulphursolution is complete, 150 parts of stearic anhycontaining residues which affect the stability of dride are introduced together with 0.5 part of the derivatives. Metal halides, especially ferric, zinc chloride and 0.5 part of hydrochloric acid. stannic and zinc chlorides, particularly ,when used The reaction mixture is maintained at a temin conjunction with hydrochloric acid, have been perature of C. for about 2 hours after which found tobevery'valuable catalysts for the esterifiit is p d into b ing w er o flash Ofl the cation of cellulose others since they render it ethylene dichloride and the mixture of etherpossible to obtain substantially complete esterifiester and stearic acid is then washed repeatedly cation of the free hydroxy groups withoutcausto with an aqueous sodium carbonate solution coning an undue amount of degradation, so that taming from 0.2 to 0.5% of sodium carbonate products havingalow moisture regain maybe obat a temperature of about C. until all the tained.- stearic acid is neutralised and removed. The

Preferably an esteriilcation medium is employed ether-ester can then be separated from the wash- 6 1118 liquid and dried.

Instead of separating the ester-ether by pourchloride has been vaporised. The product, whichcontains stearic acid aswell as the ethyl cellulose stearate. forms a liquid or semi-plastic mass which is washed with 70% aqueous ethyl alcoholat about 60-'70 C. with vigorous stirring. When the washings are no longer acid the plastic mass is cooled and as much of the liquid as possible removed, for example by pressure. The mass is then dissolved in acetone and the solution poured into cold water whereupon a semiflbrous precipitate is obtained which is separated and dried at about 30 C. Further purification of the precipitate, if necessary, can be eflected by washing with a dilute solution of sodium carbonate or other alkali to remove residual stearic acid in the form of its salt. The mass can then be further washed with hot water and dried. t An important property of the cellulose etheresters such as are obtained according to the previous example is the large number and variety of organic liquids in which they are soluble.

' For example, an ethyl cellulose stearate can be .obtained according to the example which is soluble in' methyl ethyl ketone, acetone, methyl and ethyl acetates, benzene, toluene, xylene, chloroform, methylene and ethylene dichlorides, butyl alcohol and diethyl ether. Its moistureregain is only about 5% of that of commercial cellulose acetate and less than 20% of that of the original ethyl cellulose.

The cellulose derivatives obtained by the probess of the present invention may be used in the form of solutions or plastic compositions for numerous purposes, particularly purposes for which a good water-resistance and low moisture-regain is important. For instance, they maybe employed for the insulation of electric wires, cables, condensers and other electrical apparatus, for water-proofing fabrics or wrapping foils or as basic materials for filaments, foils and other articles.

Having described my invention, what I desire to secure by Letters Patent is:

1. Process 'for the production of cellulose derivatives, which comprises esterifying cellulose ethers at temperatures up to 50 C. with anhydrldes of organic carboxylic acids containing at least six carbon atomsin the molecule in the presence of metal halides'and a hydrogen halide as catalysts.

2. Process according to claim 1, wherein a cellulose ether containing at least two alkyl radicles per CsHmOs unit of cellulose is esterified.

3. Process for the production of cellulose derivatives, which comprises esterifying cellulose ethers at a temperature up to 50 C. with anhydrides of organic carboxylic acids containing at least 6 carbon atoms in the molecule in the presence of a hydrogen halide andof a metal halide 4 molecule inthe presence of a catalyst consisting of a mixture of a hydrohalide acid and a metal halide selected from the group consisting of stannic, zinc and ferrie'halides, the said acid and said halide being each present in a proportion of from 0.25 to 1% of the weight of the cellulose ether.

5. Process for the production of cellulose derivatives, which comprises esterifying at a temperature of 50 C. acellulose ether containing at least 2 alkyl radicles per CsHmOs unit of cellulose in a .medium "which is a solvent for the cellulose ether and for the ether-ester produced, with an anhydride of a fatty acid containing at least 6 carbon atoms in .the molecule in the presence of a catalyst consisting of a mixture of hydrochloric acid and a, metal chloride selected from the group consisting of stannic, zinc and ferric chlorides, the said acid and said chloride being each employed in a proportion of from 0.25 to 1% of the weight of the cellulose ether.

6. Process for the production of cellulose derivatives, which comprises esterifying at a temperature of 50 C.- a cellulose ether containing at least 2 alkyl radicles per CsHloOs unit of cellulose, in a medium which is a solvent for the cellulose ether and for the ether-ester produced, with an anhydride of a fatty monocarboxylic acid containing at least 12 carbon atoms in the molecule in the presence of a catalyst consisting of a mixture of hydrochloric acid and a metal chloride selected from the group consisting of stannic, zincv and ferric chlorides, the said acid and said chloride being each present in'a proportion of from 0.25 to 1% of the weight of the cellulose ether.

7. Process for the production of cellulose .derivatives, which, comprises esterifying at a temperature of 50 C. an ethyl cellulose containing at least 2 ethyl radicles per CsHmOs unit of cellulose, in a medium which is a solvent for the ethyl cellulose and for the ether-ester produced,

of the ethyl cellulose.

with an anhydride of a fatty acid containing at" least 6 carbon atoms in the molecule in an amount not exceeding of that theoretically required to efiect the desired degree of esterification and in the presence of a catalyst consisting of a mixture of hydrochloric acid and a metal chloride selected from the group consisting of stannic, zinc and ferric chlorides, the said acid and said chloride being each present in a proportion of from 0.25 to 1% of the weight of the ethyl cellulose;

8. Process for the production of cellulose derivatives, which comprises esterifyingat a temperature of 50 C. ethyl cellulose containing at least 2 ethyl radicles per CsHmOs unit of cellulose, in a medium which is a solvent forthe ethyl cellulose and for the ether-ester produced, with an anhydride of a fatty monocarboxylic acid containing at least 12 carbon atoms in the molecule in anamount not exceeding 110% of that theoretically required to effect the desired degree of esterification, in the presence of a catalyst consisting of a mixture'of hydrochloric acid and a metal chloride selected from 'the group consisting of stannic, 'zinc and ferric chlorides, the said acid and said chloride being each employed in a proportion of from 0.25 to 1% of the weight 9. Process for the production of cellulose derivatives, which comprises esterifying at a temperature of 50 C. ethyl cellulose containing at least 2 ethyl radicles per CaHmOs unit of cellulose, in a medium which is a solvent for the ethyl cellulose and for the ether-ester produced, with stearic anhy r de in amount not exceeding 110% STATES PATENTS of that theoretically required t effectthe desired N r a e te degree of esteriflcatlon, in the presence of a. cat- ,0 2 D eyf M 12 10. 1936 alyst consisting of a mixture of hydrochloric acid 6 FOREIGN PATENTS and a metal chloride selected from the group 7 consisting of stannlc,v zinc and ferric chlorides, Number counmthe said acid and said chloride being each em- 300,942 Great Britain 1928 ployed in a proportion 'Of from 0.25 to 1% of the m OTHER REN weight of the ethyl cellulose Cellulose Chemistry," Heuser, 1944, pages JAMES WO'I'I-IFBSPQ N REFERENCES CITED The following references are of record in the file of this patent: I 15 237-238. (John Wiley '8: Sons Inc.) v 

